201132694 六、發明說明： 【考务明戶斤屬^:冬奸々貝】 參考相關申請案 本申請案係請求於2009年9月22曰所提申之美國臨時 申請案第61/244,618號之優惠，該臨時申請索之内容係整體 於此併入本案作為參考。 發明領域 本發明係關於可撓的經模製或經擠製塑膠物件。在一 實施態樣巾，本發明係關於半導體可撓的_製或經擠製 塑膠物件，然而在另一方面，本發明係關於用於製造此等 物件的方法。在又一方面，本發明係關於包含一或多個含 有傳導性碳黑之混合物以及不相同之彈性體化合物之調八 物之成份的此類物件。 發明背景 在電力纜線連接器應用中，一所欲之特徵是連接器之 可撓性用以易於安裝。這對於所謂預封型滑接型連接器是 特別重要的’滑接型連接器並非是工廠預拉型並且其需要 一牛固的女裝以預防濕氣進入至該規線連接處（其可導致 電氣失效）。 這些連接器一般係包含一内半導體層、一較厚之絕緣 層以及一覆蓋該部件整體之外半導體層。該半導體層之所 欲的傳導性級別係藉由該材料之體積電阻率而量測，該用 於此類型應用之材料的體積電阻率係少於(<)1000歐姆/公 £ 3 201132694 分(〇hms、em)，且較佳係〈谓歐姆公分。較佳地在徵線 運作之情形下（-般係〇至95。〇該體積電阻率係穩定。 對於一由三元乙丙橡膠單體(EPDM)為基礎之材料而 製成的典型部件，祕達到所要求之體積電阻率所需的傳 導性锬黑的量-般敍於(>)3G重“分比（重量百分比）。 此係大家所知的展透閾值。因為碳黑作用為一補強劑，此 傳導性填㈣的層級可明顯地使崎制可撓性減少至該 半導體層相較於該絕緣層為非常堅硬之程度。換句話說， 所完成之經模製的部件的可撓性係因為外半導體及内半導 層較向的堅硬度而嚴重地受到折衷。 使用塑化油以及蠟以改善可撓性之調配物方法係在文 獻中已知的，但在教學及教示中一般卻是有限的。因此， 存在對於改善半導體層可撓性之技術的需要以改善整體部 件的可撓性，然而也將該纜線之所欲的體積電阻率維持在 所預期的運作狀態。一個方法係使用以非聚烯烴為基礎的 樹脂，例如：用於半導體複合物之聚矽氧烷橡膠。此種技 術存在且在使用中，例如，在所謂的冷收縮連接器中。然 而’此種材料的成本相較於以聚稀煙為基礎之複合物的成 本係明顯地來得高。此外，聚矽氧烷橡膠的撕裂強度相較 於聚烯烴橡膠材料之撕裂強度一般係較低。 【發明内容:J 發明概要 在一實施態樣中，本發明係所提供的是一經模製或經 擠製之包含至少一絕緣層以及至少一半導體層的物件，該 201132694 半導體層以重量百分比計包含： A. 1至30重量百分比的傳導性填充劑； B. 10至90重量百分比的非烯烴類彈性體； C. 10至90重量百分比的烯烴類彈性體；以及 D. 可擇地，0.5至2.5重量百分比的過氧化物。 在一實施態樣中，該填充劑係傳導性碳黑及/或金屬顆 粒或粉末。在一實施態樣中，該非烯烴類彈性體係聚矽氧 烷及/或胺甲酸酯橡膠。在一實施態樣中，該烯烴類彈性體 係一乙丙橡膠及/或一 EPDM橡膠。 在一實施態樣中，本發明係一包含有一半導體層之喷 射經模製物件。在一實施態樣中，本發明係一包含有在内 及外（或是第一及第二）半導體層之間的一絕緣層的噴射模 製電氣連接器，典型地該絕緣層係和該内及外半導體層二 者直接接觸。該電氣連接器典型地具有少於1,000歐姆-公分 之體積電阻率，較佳地係少於500歐姆-公分。 在一實施態樣中，本發明係一包含有該半導體層之經 擠製物件。在一實施態樣中，本發明係一包含有在内及外 (或是第一及第二）半導體層之間的絕緣層的具可撓性屏蔽 纜線，典型地該絕緣層係和該内及外半導體層二者直接接 觸。該電氣連接器典型地具有少於1,000歐姆-公分之體積電 阻率，較佳地係少於5〇〇歐姆-公分。 在一實施態樣中，本發明係一半導體組成物，以重量 百分比計其包含： A.1至30重量百分比的傳導性填充劑； 201132694 B. U)至90重量百分 C. 10至9Gf量百分萍性體， 、烯蛵類彈性體；以及 D. 可擇地，〇.5至2 5 汉 【實施方式】 里百为比的過氧化物。 較佳實施例之詳細說明 除非另外有所陳明、上 術領域中為慣例的，所_ 中觸含的，或是在該技 礎，而且所有的測試方法係^从及百分比係以重量為基 用的。用於美國專利實務之目^露内容之提申日當時所通 請或是公開案的内容係整體併入=何參考專利、專利申 美國版本係也如此作為參考 Φ為參考（或是其等效之 (對於那姊在此揭露巾㈣是胁合成技術、定義 及在技術領域中之，的揭=定義不-致的範圍)以 範圍中之數值範圍係約略的，而因此可包括在此 ，除非另时所㈣。數值_包括所有的值 3較小及較大的值，在增加—單位時，所提供的是在 任Γ值及糾較高值之間有至少二單位之分別。作為 巳例’如果—組合、物理或其它性質，舉例來說，例如： ^子量、點性、融化指數等等，係自刚至！，麵其係意 ^所有的個別的數值’例如⑽、⑻、iQ2等等以及次级 " 例如· 100至144、155至170、197至200等等，係明 確〜被卿。對於含有少糾之值或是含有零分之大於^的 之(例如.1.1、1.5等等）範圍，在合適時，一單位係被 為是0.0001、0 ’、〇.〇1或是〇·ι。對於含有少於1〇之單 6 201132694 個位數數字之範圍（例如1至5)，典型地一單位被視為是 0.1。這些僅是特別用於指出的範例，且經列舉之在最低值 及最高值之間的數值所有可能的組合係被認為是明顯陳述 在此揭露中。除了別的以外，在此揭露中之數字範圍係提 供用於該組成物之成份量以及該等組成物成份的各種特 性。 「纜線」及相似的用詞表示在一保護絕緣體、保護套 或是鞘套之内之至少一電纜或是光纖。典型地，一纜線係 二或更多之綁在一起的電纜或光纖，典型地係在一通用之 保護絕緣體、保護套或是鞘套之内。在一保護套内之個別 的電纜或光纖係裸露的、隱蔽著的或是隔絕開的。組合式 纜線可包含電纜及光纖二者。該纜線等可經設計用於低、 中及高電壓應用。典型纜線設計係陳述在美國第 5,246,783、6,496,629以及6,714,707號專利。 「聚合物」表示一藉由使單體反應（也就是聚合化反 應）(不論是相同的或是不同類型）而製備之化合物。該通用 用詞聚合物因此包含用詞「同聚物」以及用詞「互聚物（互 聚物）」；「共聚物」通常應用於意指只由一類型之單體所 製備之聚合物，而「互聚物」則如下所定義。 「互聚物」以及「共聚物」指的是藉由至少二種不同 類型之單體聚合物反應而製備的聚合物。這些通用用詞包 括傳統之共聚物（由二種不同類型之單體所製備之聚合物） 以及由多於二種不同類型之單體所製備之聚合物（例如：三 元共聚物、四元共聚物等等）二者。201132694 VI. Description of the invention: [Certificate of the Ming Dynasty]: the winter rape mussels. Refer to the relevant application. This application is filed on September 22, 2009, and the US provisional application No. 61/244,618 The offer, the content of the provisional application is incorporated herein by reference in its entirety. FIELD OF THE INVENTION This invention relates to flexible molded or extruded plastic articles. In one embodiment, the present invention relates to semiconductor flexible or extruded plastic articles, however, in another aspect, the present invention relates to methods for making such articles. In yet another aspect, the invention is directed to such articles comprising one or more components comprising a mixture of conductive carbon black and a different elastomeric compound. BACKGROUND OF THE INVENTION In power cable connector applications, a desirable feature is the flexibility of the connector for ease of installation. This is especially important for so-called pre-sealed slip-type connectors. The slip-type connector is not factory pre-tensioned and it requires a cowhide to prevent moisture from entering the gauge connection. Causes electrical failure). These connectors typically comprise an inner semiconducting layer, a thicker insulating layer, and a semiconductor layer overlying the component as a whole. The desired conductivity level of the semiconductor layer is measured by the volume resistivity of the material, and the volume resistivity of the material used for this type of application is less than (<) 1000 ohms/m 3 201132694 cents (〇hms, em), and preferably is < ohm ohm. Preferably, in the case of a line operation (typically 95 to 95. The volume resistivity is stable. For a typical part made of EPDM based material, The amount of conductive darkness required to achieve the required volume resistivity is generally referred to as (>) 3G heavy "parts by weight (% by weight). This is known as the spread threshold. Because carbon black is A reinforcing agent, the level of this conductive fill (4) can significantly reduce the roughness flexibility to the extent that the semiconductor layer is very hard compared to the insulating layer. In other words, the finished molded part Flexibility is severely compromised by the relatively stiffness of the outer semiconducting and inner semiconducting layers. Methods for using plasticized oils and waxes to improve flexibility are known in the literature, but are taught and The teachings are generally limited. Therefore, there is a need for techniques to improve the flexibility of the semiconductor layer to improve the flexibility of the overall component, but also maintain the desired volume resistivity of the cable at the desired operation. State. One method is used Olefin-based resins, such as polyoxyalkylene rubbers for semiconductor composites. This technology exists and is used, for example, in so-called cold shrink connectors. However, the cost of such materials is comparable to The cost of the composite based on poly-smoke is obviously higher. In addition, the tear strength of the polyoxyalkylene rubber is generally lower than that of the polyolefin rubber material. [Summary: J invention BRIEF DESCRIPTION OF THE DRAWINGS In one embodiment, the present invention provides a molded or extruded article comprising at least one insulating layer and at least one semiconductor layer, the 201132694 semiconductor layer comprising: A. 1 to 30% by weight of conductive filler; B. 10 to 90% by weight of non-olefinic elastomer; C. 10 to 90% by weight of olefinic elastomer; and D. Alternatively, 0.5 to 2.5 weight percent Oxide. In one embodiment, the filler is a conductive carbon black and/or metal particle or powder. In one embodiment, the non-olefinic elastomeric polyoxane and/or urethane rubber In one embodiment, the olefin-based elastomeric system is an ethylene-propylene rubber and/or an EPDM rubber. In one embodiment, the invention is a spray-molded article comprising a semiconductor layer. In one aspect, the invention is an injection molded electrical connector including an insulating layer between the inner and outer (or first and second) semiconductor layers, typically the insulating layer and the inner and outer layers The semiconductor layers are in direct contact with each other. The electrical connector typically has a volume resistivity of less than 1,000 ohm-cm, preferably less than 500 ohm-cm. In one embodiment, the invention includes An extruded article of a semiconductor layer. In one embodiment, the invention is a flexible shielded cable comprising an insulating layer between the inner and outer (or first and second) semiconductor layers, Typically the insulating layer is in direct contact with both the inner and outer semiconductor layers. The electrical connector typically has a volume resistivity of less than 1,000 ohm-cm, preferably less than 5 ohm-cm. In one embodiment, the invention is a semiconductor composition comprising, by weight percent: A. 1 to 30 weight percent of conductive filler; 201132694 B. U) to 90 weight percent C. 10 to 9 Gf Amounts of bismuth, an olefinic elastomer; and D. alternatively, 55 to 2 5 Han [embodiment] a ubiquitous ratio of peroxide. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Unless otherwise stated, conventional in the field of art, or in the context of the art, all test methods are based on weight and percentage Base. For the purpose of the US patent practice, the content of the disclosure or disclosure of the contents of the disclosure is the overall integration = the reference patent, the patent application, the US version is also used as a reference Φ for reference (or its etc.) The effect is that the scope of the range is numerically approximated and can therefore be included here. Unless otherwise (4). The value _ includes all the smaller and larger values of the value 3. In the case of increasing - the unit, there is a difference of at least two units between the Γ value and the higher value. For example, if - combination, physical or other properties, for example: ^ sub-quantity, point, melting index, etc., from the beginning to the end, the system is intended to ^ all individual values 'for example (10), (8), iQ2, etc., and secondary " for example, 100 to 144, 155 to 170, 197 to 200, etc., are clear ~ being clear. For values that contain less correction or contain zeros greater than ^ (for example .1.1, 1.5, etc.) range, when appropriate, a unit is considered to be 0.0001, 0 ', 〇.〇1 or 〇·ι. For ranges containing less than 1〇 of the single 6 201132694 single digit number (eg 1 to 5), typically one unit is considered to be 0.1. These are only It is specifically intended to be illustrative, and all numerical combinations of the numerical values listed between the minimum and maximum values are considered to be expressly disclosed herein. The numerical ranges disclosed herein are, among others, The amount of ingredients used in the composition and the various characteristics of the components are provided. "Cable" and similar terms mean at least one cable or fiber within a protective insulator, protective sheath or sheath. Typically, a cable is two or more cables or fibers that are tied together, typically within a common protective insulator, protective sleeve or sheath. Individual cables or fibers within a protective casing It is bare, concealed or isolated. The modular cable can contain both cable and fiber. The cable can be designed for low, medium and high voltage applications. Typical cable design is stated in the US 5,246,783, 6,496,629 And the patent No. 6,714,707. "Polymer" means a compound prepared by reacting a monomer (that is, a polymerization reaction) (whether the same or different types). The generic term polymer thus includes the word " "Homopolymer" and the term "interpolymer (interpolymer)"; "copolymer" is generally used to mean a polymer prepared from only one type of monomer, and "interpolymer" is as defined below. "Interpolymer" and "copolymer" refer to polymers prepared by the reaction of at least two different types of monomeric polymers. These general terms include traditional copolymers (from two different types of singles). The polymer prepared by the body) and the polymer (for example: terpolymer, tetrapolymer, etc.) prepared from more than two different types of monomers.
S 7 201132694 「烯烴類」及相似用詞表示一具有一或多個雙鍵之不 飽和、脂肪族或是環脂族，經取代或是未經取代烴類。「經 取代烯烴類」表示一烯烴其中一或多個連接至該烯烴之任 何碳之氫原子係被另一基團所取代，例如：鹵素、芳香基、 經取代之芳基、環烷基、經取代之環烷基、雜環烷基、經 取代之雜環炫基、_素、_烧基、說基、鱗橋基、烧氧基、 胺基、硫基、或是此類取代基之一或多個的組合。 「彈性體」及相似用詞"表示一可被拉伸至至少二倍其 原始長度之類橡膠聚合物，且當執行拉伸的力量釋放時其 非常快速地回縮至近乎其原始長度。一彈性體具有約 10,000巴斯卡（psi)(68.95MPa)或較少之彈性係數而且在室 溫下之未交聯狀態通常多於200%之延長，使用ASTM D638-72. EP274888之方法量測時。 「烯烴類彈性體」及相似用詞表示包含至少50莫耳百 分比（mol%)之衍生自一或多種烯烴之單元的彈性體聚合 物。 「非烯烴類彈性體」及相似用詞表示包含至少50莫耳 百分比之衍生自除了烯烴以外之單體的單元的彈性體聚合 物。 「乙烯彈性體」及相似用詞表示一包含有至少50莫耳 百分比之衍生自乙烯之單元的彈性體聚合物。 「摻合物」、「聚合物摻合物」及相似用詞表示二或 多種聚合物之摻合物。此類之摻合物可以是可混溶的或是 不可混溶的。此類之摻合物可以是相分離的或是非相分離 201132694 的。此類之換合物可以包含或是不包含一或多種域配置， 在由穿透式電子顯微鏡、光散射、X-射線散射以及任何其 它該技術領域中已知之方法來測定時。 「組成物」及相似用詞表示二或多種成份之混合物或 摻合物。例如，在本發明製備一半導體喷射模製物件之内 文中，一組成物係包括至少一傳導性填充劑、至少一非烯 烴類彈性體、至少一烯烴類彈性體以及至少一自由基起始 劑。 「經交聯的」、「經固化的」以及相似的用詞表示該 聚合物在其被塑形為一物件之前或之後係經過或是被曝露 在一引發交聯反應之處理下，且具有在40及100重量百分比 之間之可萃出二甲苯或是十氫萘(也就是，多於或等於40重 量百分比之膠成份）。 「可交聯的」、「可固化的」及相似用詞表示該聚合 物在其被塑形為一物件之前或之後並非是經固化的或是經 交聯的且並未經過或是被曝露在一引發實質交聯反應之處 理下，即使該聚合物包含在經過或是曝露於此處理下將造 成、促進或是使得實質交聯之添加劑或是官能性(例如曝露 於水）。 烯烴類彈性體 使用於實施本發明之烯烴類彈性體包括聚烯烴共聚物 以及互聚物二者。聚烯烴共聚物之範例係乙烯和丙烯之共 聚物。聚烯烴互聚物之範例係乙烯/α-烯烴互聚物以及丙烯 /α-稀烴互聚物。該α-稀烴較佳係一C3_2Q鏈形、支鏈或環狀α- 9 201132694 烯烴（對於烯/(X-烯烴互聚物，乙烯係被認為是一 α_烯烴）。 CyG α-烯烴之範例包括丙烯、ι_丁稀、4_甲基_丨戊稀、1 己烯、1-辛烯、卜癸烯、卜十二烯、丨_十四烯、^十六烯以 及1-十八烯。該V-烯烴也可以含有一環狀結構，例如：環 己烷或環戊烷，造成一α-烯烴，例如：3_環己基_丨_丙烯(烯 丙基環己烷）以及乙烯基環己烷。雖然不是該用詞標準概念 t的α-烯烴，對於本發明的目的，特定環狀烯烴(如：降伯 烯及相關烯烴)係α-烯烴且可以被使用為代替某些或是所有 的上述V-烯烴。相同地，用於本發明之需求，苯乙烯及其 相關烯烴(例如：V-甲基苯乙烯等等）係α-烯烴。說明性之聚 烯烴共聚物包括乙烯/丙烯、乙烯/丁烯、乙烯/1-己烯、乙烯 /1-辛烯、乙烯/苯乙烯等等。說明性之三元共聚物包括乙烤 /丙烯71'辛烯、乙烯/丙烯/丁烯、乙烯/丁烯/1-辛烯以及乙烯 /丁烯/笨乙烯。該共聚物可以是無規則的或是嵌段式的。 該稀煙類彈性體也可包含一或多種官能基，例如：不 飽和醋或醆’且這些彈性體（聚烯烴）係已知的且可藉由習知 之南壓技術而製備。該等不飽和酯類可以是烷基丙烯酸 酯、烷基甲基丙烯酸酯、或是乙烯羧酸酯。該烷基可具有1 至8個奴原子且較佳係具有1至4碳原子。該羧基可具有2至8 個石反原子且較佳係具有2至5個碳原子。貢獻於該酯類共聚 單體之共聚物部份以重量計可以是在1高達50百分比的範 圍内’以該共聚物之重量為基礎。丙烯酸酯以及甲基丙烯 酸醋之範例係丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸f酯、 丙烯酸第二丁酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、以 10 201132694 及2-乙基己基丙烯酸酯。乙烯羧酸酯之範例係乙烯乙酸 酯、乙烯丙酸酯、以及乙烯乙烯丁酸酯。不飽和酸類之範 例包括丙烯酸或丁稀二酸。 官能基也可經由接枝而被包括在烯烴類彈性體中，该 接枝技術係該技術領域中普遍知道的所以可輕易完成。在 一實施態樣中，接枝可藉由自由基官能基化之方法而進 行，其典型地包括熔融摻合一烯烴聚合物、一自由基啟始 劑(例如一過氧化物等等）以及一含有官能基之化合物。在熔 融摻合期間，該自由基啟始劑和該烯烴聚合物反應（反應性 熔融摻合）以形成聚合物基團。含有官能基之化合物連接炱 該聚合物基團之骨架以形成一官能性聚合物。示範性之含 有官能基之化合物包括但不限定於烷氧矽烷，例如：乙烯 三曱氧矽烷、乙烯三乙氧矽烷以及乙烯羧酸，以及酸酐’ 例如：順丁烯二酸酐。 使用於本發明之烯烴類彈性體更多特定之範例包括非 常低密度之聚乙烯（VLDPE)(例如：由陶氏化學公司所製造 之FLEXOMER®乙烯/1-已烯聚乙烯），同質性分枝、鏈狀之 乙烯/ V -烯烴共聚物（例如：由三井石化股份有限公司所製造 之TAFMER®以及由埃克森美孚化學公司所製造之 EXACT®)’同質性分枝、實質鏈狀之乙烯Λ/-烯烴聚合物(例 如：可由陶氏化學公司獲得之AFFINITY®以及ENGAGE® 苡乙烯），以及烯烴嵌段共聚物，例如：在美國第7,355,089 號專利中所提到的那些（例如：可由陶氏化學公司獲得之 INFUSE®)。更多較偏好之聚烯烴共聚物係同質性分枝鏈狀 11 201132694 之及實質鏈狀之乙烯共聚物。該實質鏈狀之乙烯共聚物係 特別喜愛的’且係更完整地在美國第5,272,236、5,278,272 以及5,986,〇28號專利中敘述。 使用於貫施本發明之稀烴類彈性體也包括丙稀'丁稀 及其匕以烯類為基礎之共聚物，例如：包含有大部份由丙 稀行生而來之單元以及小部份由另一α-稀烴（包括乙烯）衍 生而來之單元的共聚物。使用於實施本發明之示範性丙烯 聚合物包括可由陶氏化學公司獲得之VERSIFY®聚合物， 、及可由埃克森美孚化學公司獲得之VISTAMAXX®聚合 物。 任何上述烯烴類彈性體之摻合物也可被使用於本發 明’且該烯煙_彈性體可和-或多種其它聚合物摻合或是 稀釋至本發明之該烯烴類彈性體(在-較佳模式中）構成至 少約5〇，較佳係至少約75且更佳係至少約8〇，重量百分比 之該摻合物之熱塑性聚合物成份的程度且維持其可撓性。 在較少偏好之模式中且依據可能探索之其它特質，該稀烴 類彈性體成份可少於5G%之熱塑性聚合物成份。 使用於實施本發明之該烯烴類彈性體，特別是乙烯彈 性體，在接枝之前典型地具有少於0.91克/每立方公分 (g/cm3)之密度，較佳係少於⑽克/立方公分。該乙稀共聚 U地_有多於0 85克/立方公分的密度，較佳係多於 0.86克/立方公分。密度係藉由ASTMD_792之步驟所測量。 -般地，該互聚物之α_烯烴成份愈多，該密度愈低且該互 聚物則愈不定形。低密度聚馳絲物—般係具有半結晶 12 201132694 性的特徵、具可撓性且具有良好之光學性質，例如： •口J見 光及紫外光之高穿透性且低混濁度。 使用於實施本發明之乙烯彈性體在接枝之前典 有多於0.10克/每10分鐘(g/ΐο分鐘）之熔融係數，較佳係夕 於1 g/io分鐘。該乙烯彈性體典型地具有少於500 &/ΐΛ \ 分鐘 之熔融係數，較佳係少於100g/10分鐘。熔融係數係藉由 ASTMD-1238 (190°C/2.16公斤）之步驟所測量。 該烯烴類彈性體典型係使用為在自10至90重量百八比 範圍的量，以該組成物之重量為基礎。較佳地，該歸炉類 彈性體係使用為自20至80重量百分比範圍的量，較佳係自 25至50重量百分比範圍的量，以該組成物之重量為基礎 非烯烴類彈性體 使用於實施本發明之非烯烴類彈性體包括聚石夕氧燒以 及胺甲酸酯彈性體、苯乙烯-丁二烯橡膠(SBR)、腈橡膠、 氯丁二烯、氟彈性體、全氟代彈性體、聚醚嵌段醯胺以及 氯磺化聚乙烯。該聚矽氧烷彈性體係聚有機矽氧烷且典型 八有平均單元化學式RaSiC^4·#2，其可具有一鍵狀或是部 份分枝之結構，但較佳係為鏈狀。每個尺可以是相同的或是 不同的。R係經取代或是未經取代之單價羥基，舉例來說， 八叮以疋燒基，如：甲基、乙基、丙基、丁基及辛基； 一芳香基，如：苯基及甲苯基；一芳烷基；一烯基，如： 乙烯基、烯丙基、丁烯基、己烯基及庚烯基；以及一經鹵 化之烷基，如：氣丙基及3,3,3-三氣丙基。該聚有機矽氧烷 可月b以任何上述之基團或是以一羥基做為尾端。當r為一烯 13 201132694 基時，該烯基較佳係為乙稀基或己烯基。事實上，稀某可 出現在該聚有機石夕氧燒之端基圏及/或聚合物的側鏈/ 不限2社㈣氧歸膠#聚有機錢燒包括，但並 甲基石^ — ?基乙埽基錢之聚二甲基砂氧燒、端三 矽：产一甲基矽氧烷、甲基乙烯基矽氧烷和二甲基 ^端三甲基料共聚物、甲基乙烯基錢烧和二甲 基石夕钱之端二甲基乙烯基錢共聚物、端二甲基經基石夕 乳之聚二甲切纽、甲基乙烯基魏灿二甲基石夕氧烧 之端二甲基隸錢共聚物、甲基乙稀切纽和二甲基 石夕氧燒之端甲基乙稀基經基錢共聚物、端二甲基已稀基 矽氧之聚二曱基矽氧烷、甲基己烯基矽氧烷和二曱基矽氧 烷之端三甲基矽氧共聚物、曱基己烯基矽氧烷和二甲基矽 氧烷之端二曱基己基矽氧共聚物、曱基苯基矽氧烷和二曱 基石夕氧燒之端二甲基乙烯基石夕氧共聚物、曱基笨基石夕氧烷 和二曱基矽氧烷之端二甲基己基矽氧共聚物、甲基(3,3,3_ 三氟苯基）矽氧烷和二甲基矽氧烷之端二甲基乙烯基矽氧 共聚物、以及曱基(3,3,3-三氟苯基)矽氧烧和二甲基矽氧烧 之端二甲基己基矽氧共聚物。 該胺甲酸酯彈性體係由如聚醚類和聚酯類之反應性聚 合物和異氰酸酯基官能之有機化合物而製備。一典型之範 例係二羥基官能聚醚及/或三羥基官能聚醚和曱苯二異氰 酸醋之反應產物，因此所有的羥基係經反應的以形成胺甲 酸酯鏈結而留下異氰酸酯基用於進一步的反應。此類型之 反應產物係稱為一預聚合物’其於曝露於濕氣之下可自行 14 201132694 固化或是藉由化學計量添加聚卡必醇(P〇lycarbin〇lS)或是其 它和異氰酸酯反應之多官能反應性材料。該胺甲酸酯彈性 體係商業上製備為具有各種比例之異氰酸酯化合物和_或 聚自旨。 最普遍之胺曱酸酯彈性體係那些含有羥基官能之聚喊 或聚酯以及低分子量之多官能聚合異氰酸酯。另一供使用 之帶有羥基官能之聚醚或聚酯之普遍材料係曱苯二異氰酸 。 適用之胺甲酸酯橡膠之非限制性範例包括可由路博潤 公司（Lubrizol Corporation)購得之 PELLETHANE™ 熱塑性 聚胺曱酸酯彈性體；ESTANEtm熱塑性聚胺曱酸酷， TECOFLEX™熱塑性聚胺甲酸酯，cARBOTHANE™熱塑性 聚胺甲酸酯’ TECOPHILIC™熱塑性聚胺甲酸酯， TECOPLAST™熱塑性聚胺曱酸酯，以及tec〇THANEtm熱 塑性聚胺曱酸酯，皆可由諾譽化工（N〇veon)購得； ELASTOLLAN™熱塑性聚胺甲酸酯以及其它可由BASF購 得之熱塑性聚胺甲酸酯；以及額外可由拜耳(Bayer)、亨斯 邁(Huntsman)、路博潤公司（Lubrizol Corporation)、麥金莎 (Merquinsa)以及其它供應商購得之熱塑性聚胺曱酸酯材 料。較佳之胺甲酸酯橡膠係那些所謂「可軋(millable)」胺 甲酸酯，如：由TSI工業而得之MILLATHANETM等級》 對於此類胺甲酸酯材料之額外的資訊可在Golding，S 7 201132694 "Olefins" and similar terms mean an unsaturated, aliphatic or cycloaliphatic, substituted or unsubstituted hydrocarbon having one or more double bonds. "Substituted olefin" means that one or more hydrogen atoms of any carbon bonded to the olefin are substituted by another group, for example, halogen, aryl, substituted aryl, cycloalkyl, Substituted cycloalkyl, heterocycloalkyl, substituted heterocyclyl, _ s, _ s, s, squaring, alkoxy, amine, thio, or such substituents A combination of one or more. "Elastomer" and similar terms " denotes a rubber polymer that can be stretched to at least twice its original length and which retracts very rapidly to near its original length when the force to perform the stretching is released. An elastomer having a modulus of elasticity of about 10,000 psi (68.95 MPa) or less and an uncrosslinked state at room temperature is typically more than 200% extended, using the method of ASTM D638-72. EP274888 Time measurement. "Olefinic elastomer" and like terms mean an elastomeric polymer comprising at least 50 mole percent (mol%) of units derived from one or more olefins. "Non-olefin elastomer" and like terms mean an elastomeric polymer comprising at least 50 mole percent of units derived from monomers other than olefins. "Ethylene elastomer" and like terms mean an elastomeric polymer comprising at least 50 mole percent of units derived from ethylene. "Blend", "polymer blend" and similar terms mean a blend of two or more polymers. Blends of this type may be miscible or immiscible. Such blends may be phase separated or non-phase separated 201132694. Such compounds may or may not include one or more domain configurations as determined by transmission electron microscopy, light scattering, X-ray scattering, and any other method known in the art. "Composition" and like terms mean a mixture or blend of two or more components. For example, in the context of the present invention for preparing a semiconductor injection molded article, a composition comprising at least one conductive filler, at least one non-olefinic elastomer, at least one olefinic elastomer, and at least one radical initiator . "Crosslinked", "cured" and similar terms mean that the polymer passes or is exposed to a cross-linking reaction before or after it is shaped into an article and has Between 40 and 100 weight percent, xylene or decahydronaphthalene (i.e., more than or equal to 40 weight percent of the gum component) can be extracted. "Crosslinkable", "curable" and similar terms mean that the polymer is not cured or crosslinked before or after it is shaped into an article and has not been exposed or exposed. The additive, whether or not exposed to water, will cause, promote or substantially crosslink the additive or functional (e.g., exposed to water) under a process that initiates a substantial cross-linking reaction, even if the polymer comprises, after exposure to or exposure to the treatment. Olefin-Based Elastomer The olefin-based elastomer used in the practice of the present invention includes both a polyolefin copolymer and an interpolymer. An example of a polyolefin copolymer is a copolymer of ethylene and propylene. Examples of polyolefin interpolymers are ethylene/α-olefin interpolymers and propylene/α-dilute hydrocarbon interpolymers. The α-dilute hydrocarbon is preferably a C3_2Q chain, branched or cyclic α- 9 201132694 olefin (for olefin/(X-olefin interpolymer, ethylene is considered to be an α-olefin). CyG α-olefin Examples include propylene, i-butadiene, 4-methyl-peptone, 1-hexene, 1-octene, decene, dodecene, 丨-tetradecene, hexadecene, and 1- Octadecene. The V-olefin may also contain a cyclic structure such as cyclohexane or cyclopentane to form an alpha-olefin such as 3-cyclohexyl-indene-propylene (allyl cyclohexane). And vinylcyclohexane. Although not the alpha-olefin of the standard concept t, for the purposes of the present invention, specific cyclic olefins (e.g., primary olefins and related olefins) are alpha-olefins and can be used instead. Some or all of the above V-olefins. Similarly, for the purposes of the present invention, styrene and its related olefins (e.g., V-methylstyrene, etc.) are alpha-olefins. Illustrative polyolefin copolymerization The materials include ethylene/propylene, ethylene/butene, ethylene/1-hexene, ethylene/1-octene, ethylene/styrene, etc. Illustrative terpolymers include B-bake/propylene 71 'octene, ethylene/propylene/butene, ethylene/butene/1-octene, and ethylene/butene/stupyl ethylene. The copolymer may be random or block type. It may also contain one or more functional groups, for example: unsaturated vinegar or hydrazine' and these elastomers (polyolefins) are known and can be prepared by conventional Southern Pressure techniques. The unsaturated esters may be alkane a acrylate, an alkyl methacrylate, or an ethylene carboxylate. The alkyl group may have from 1 to 8 slave atoms and preferably has from 1 to 4 carbon atoms. The carboxyl group may have from 2 to 8 stone counterions. The atom and preferably has 2 to 5 carbon atoms. The copolymer portion contributing to the ester comon may be in the range of up to 50% by weight based on the weight of the copolymer. Examples of esters and methacrylic acid vinegars are ethyl acrylate, methyl acrylate, methacrylate methacrylate, dibutyl acrylate, n-butyl acrylate, n-butyl methacrylate, 10 201132694 and 2-ethylhexyl Acrylate. Examples of ethylene carboxylate are ethylene acetate, ethylene propylene Acid esters, and ethylene vinyl butyrate. Examples of unsaturated acids include acrylic acid or butadiic acid. Functional groups may also be included in the olefinic elastomer via grafting, which is common in the art. It is known that it can be easily accomplished. In one embodiment, the grafting can be carried out by a method of radical functionalization, which typically involves melt blending an olefin polymer, a free radical initiator (eg, a a peroxide, etc.) and a compound containing a functional group. During the melt blending, the radical initiator and the olefin polymer are reacted (reactive melt blending) to form a polymer group. The compound is attached to the backbone of the polymer group to form a monofunctional polymer. Exemplary compounds containing functional groups include, but are not limited to, alkoxysilanes such as ethylene trioxane, ethylene triethoxy decane, and ethylene. Carboxylic acid, and anhydrides' such as maleic anhydride. More specific examples of olefinic elastomers useful in the present invention include very low density polyethylene (VLDPE) (eg, FLEXOMER® ethylene/1-hexene polyethylene manufactured by The Dow Chemical Company), homogenous Branch and chain ethylene/V-olefin copolymer (for example: TAFMER® manufactured by Mitsui Petrochemical Co., Ltd. and EXACT® manufactured by ExxonMobil Chemical Co., Ltd.) 'Homogeneous branch, substantial chain Vinyl ruthenium/-olefin polymers (for example: AFFINITY® and ENGAGE® ruthenium ethylene available from The Dow Chemical Company), and olefin block copolymers such as those mentioned in U.S. Patent No. 7,355,089 (for example: INFUSE®) available from The Dow Chemical Company. More preferred polyolefin copolymers are homogenous branched chains 11 201132694 and substantially chain ethylene copolymers. The substantially chained ethylene copolymers are particularly preferred and are more fully described in U.S. Patent Nos. 5,272,236, 5,278,272 and 5,986, the entire disclosure of each of each of The dilute hydrocarbon elastomers used in the practice of the present invention also include propylene's butadiene and its oxime-based copolymers, for example, containing most of the units derived from propylene and small parts. a copolymer of units derived from another alpha-dilute hydrocarbon, including ethylene. Exemplary propylene polymers useful in the practice of this invention include VERSIFY® polymers available from The Dow Chemical Company, and VISTAMAXX® polymers available from ExxonMobil Chemical Company. Any of the above olefin elastomer blends may also be used in the present invention' and the olefin-elastomer may be blended with or blended with various other polymers or diluted to the olefin elastomer of the present invention (at - In a preferred mode, it comprises at least about 5 Å, preferably at least about 75 and more preferably at least about 8 Å, by weight of the thermoplastic polymer component of the blend and maintaining its flexibility. In a less preferred mode and depending on other traits that may be explored, the dilute hydrocarbon elastomer component may be less than 5 G% thermoplastic polymer component. The olefinic elastomers used in the practice of the invention, particularly ethylene elastomers, typically have a density of less than 0.91 grams per cubic centimeter (g/cm3) prior to grafting, preferably less than (10) grams per cubic centimeter. Centimeters. The ethylene copolymerization U has a density of more than 0 85 g/cm 3 , preferably more than 0.86 g/cm 3 . Density is measured by the procedure of ASTM D_792. Generally, the more the alpha olefin component of the interpolymer, the lower the density and the more amorphous the interpolymer. Low-density poly-strands generally have the characteristics of semi-crystalline 12 201132694, flexible and have good optical properties, such as: • High visibility and low turbidity of light and ultraviolet light. The ethylene elastomer used in the practice of the invention typically has a melting coefficient of more than 0.10 g per 10 minutes (g/ΐ ο minutes) prior to grafting, preferably at 1 g/io minutes. The ethylene elastomer typically has a melt coefficient of less than 500 & / ΐΛ \ minutes, preferably less than 100 g/10 minutes. The melting coefficient is measured by the procedure of ASTM D-1238 (190 ° C / 2.16 kg). The olefin elastomer is typically used in an amount ranging from 10 to 90 parts by weight, based on the weight of the composition. Preferably, the furnace-type elastic system is used in an amount ranging from 20 to 80% by weight, preferably in an amount ranging from 25 to 50% by weight, based on the weight of the composition, based on the weight of the composition. Non-olefinic elastomers embodying the present invention include polyoxoxime and urethane elastomers, styrene-butadiene rubber (SBR), nitrile rubber, chloroprene, fluoroelastomers, perfluoroelastomers Body, polyether block decylamine and chlorosulfonated polyethylene. The polyoxyalkylene elastomeric system polyorganosiloxane and typically has an average unit chemical formula of RaSiC^4·#2, which may have a bond-like or partially branched structure, but is preferably chain-shaped. Each ruler can be the same or different. R is a substituted or unsubstituted monovalent hydroxy group, for example, an oxime group such as methyl, ethyl, propyl, butyl and octyl; an aromatic group such as phenyl and a tolyl; an aralkyl group; an alkenyl group such as: a vinyl group, an allyl group, a butenyl group, a hexenyl group, and a heptenyl group; and a halogenated alkyl group such as a gas propyl group and 3, 3, 3-trimethyl propyl. The polyorganosiloxane may be in the form of any of the above groups or a terminal hydroxyl group. When r is a monoene 13 201132694 group, the alkenyl group is preferably an ethylene group or a hexenyl group. In fact, the rare one can appear in the side chain of the polyorganisms and/or the side chain of the polymer / not limited to 2 (4) oxygen-based rubber #聚有机钱烧包括, but methyl stone ^基 埽 埽 钱 之 聚 聚 矽 、 、 、 、 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽钱 烧 和 和 二 二 和 和 和 和 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基a terminal dimethyl ketone copolymer, methyl ethene ruthenium and dimethyl oxalate, a methyl methacrylate group, a dimethyl dimethyl hydride group a terminal trimethyl oxime copolymer of a decyl alkane, a methylhexenyl decane and a dimethyl oxoxane, a decylhexenyl oxyalkylene, and a terminal dimethyl hexyl dimethyl methoxide Hexaoxy copolymer, nonylphenyl methoxy oxane and dimercapto oxaxy oxy-terminated dimethyl vinyl oxime copolymer, fluorenyl styryl oxa oxane and dimercapto fluorene end dimethyl Hexyloxy copolymer, A a terminal dimethylvinyloxime copolymer of (3,3,3_trifluorophenyl)anoxane and dimethyloxane, and a fluorenyl (3,3,3-trifluorophenyl)oxime A dimethyl hexyl oxime oxy-copolymer which is calcined and dimethyloxoxime. The urethane elastomer system is prepared from reactive polymers such as polyethers and polyesters and isocyanate-functional organic compounds. A typical example is the reaction product of a dihydroxy functional polyether and/or a trihydroxy functional polyether and decyl diisocyanate, whereby all of the hydroxyl groups are reacted to form a carbamate chain leaving an isocyanate. The base is used for further reactions. This type of reaction product is called a prepolymer. It can be cured by exposure to moisture or by stoichiometric addition of carbitol (P〇lycarbin〇lS) or other reaction with isocyanate. A polyfunctional reactive material. The urethane elastomer system is commercially prepared to have various ratios of isocyanate compounds and/or poly. The most common amine phthalate elastomer systems are those having a hydroxy-functional poly-polymer or polyester and a low molecular weight polyfunctional polymeric isocyanate. Another common material for the use of hydroxyl functional polyethers or polyesters is phthalic acid diphenyl isocyanate. Non-limiting examples of suitable urethane rubbers include PELLETHANETM thermoplastic polyamine phthalate elastomers available from Lubrizol Corporation; ESTANEtm thermoplastic polyamine phthalic acid cool, TECOFLEXTM thermoplastic polyurethane Acid ester, CARBOTHANETM thermoplastic polyurethane 'TECOPHILICTM thermoplastic polyurethane, TECOPLASTTM thermoplastic polyurethane phthalate, and tec〇THANEtm thermoplastic polyurethane amide, all from N〇veon Acquired; ELASTOLLANTM thermoplastic polyurethanes and other thermoplastic polyurethanes available from BASF; and additionally by Bayer, Huntsman, Lubrizol Corporation, A thermoplastic polyamine phthalate material available from Merquinsa and other suppliers. Preferred urethane rubbers are those known as "millable" urethanes, such as the MILLATHANETM grade from the TSI industry. Additional information on such urethane materials is available in Golding,
Polymers and Resins，文諾斯川（Van Nostrande)，1959，第 325頁以及之後k料等等，和桑德思和費瑞斯（Saunders and 15 201132694Polymers and Resins, Van Nostrande, 1959, page 325 and later, etc., and Sanders and Ferris (Saunders and 15 201132694)
Frisch)之聚胺曱酸酯文章，於「化學及科技」一書，第η 冊 ’ Interscience出版社，1964等等。 該聚矽氧烷和胺曱酸酯橡膠可單獨被使用或是和彼此 合併使用’且典型地使用為自90至1〇重量百分比範圍的 量’以該組成物之重量為基礎。較佳地，以該組成物之重 量為基礎，該橡膠係被使用為自80至20重量百分比範圍的 量，更佳係自50至70重量百分比。 傳導性填充劑 任何將給予少於1，〇〇〇歐姆-公分之體積電阻率至該半 導體組成物的傳導性填充劑，較佳係少於500歐姆-公分且 更佳係少於250歐姆-公分，可被使用於實施本發明。代表 性之傳導性填充劑包括但並不限定於傳導性碳黑以及金屬 顆粒。傳導性碳黑可擇自於列於ASTMD-1765-76之碳黑中 的任一者，其中包括依據ASTM稱號而如此列出之碳黑： N110 N242 N326 N358 N568 N765 N121 N270 N327 N363 N601 N774 N166 N285 N330 N375 N650 N785 S212 N293 N332 N440 N660 N787 N219 N294 N339 N472 N683 N880 N220 S300 N347 N539 N741 N907 N231 S301 N351 N542 N754 N990 N234 S315 N356 N550 N762。當然，任何其它 具相似本質之碳黑且其係適用且有效使用於橡膠複合，例 如：Ketjenblack EC、Vulcan C及XC碳黑、乙炔碳黑以及其 它所謂「傳導性碳黑」、相似於任何上述之較新但可能被 配了其它的名稱之碳黑，以及混合物也可被包括在可使用 於實施本發明之傳導性碳黑中。 16 201132694 在一實施態樣中，該碳黑係石墨烯，例如：石墨、奈 米碳管及/或富勒烯或是其和其它碳黑之混合物。此類材料 之平均顆粒尺寸典型係在奈米尺度之部份。 可擇地單獨，或是和一碳黑，至少一具傳導本質之金 屬粉末或顆粒可被使用為傳導性填充劑。這些金屬粉末或 顆粒典型地具有0.1至100微米之平均粒子尺寸，更典型係 0.3至30微米，以X-光譜線加寬法量測。金屬顆粒/粉末可具 有所欲之任何粒子外形，雖然如同已知的，該外形之選擇 係依據對於該經金屬填充產物之所預期的最終用途而決 定。可使用球形外形、板形、棱柱外形、細絲狀等等。 單獨或是和一或多種其它此類金屬混合或是微細粉末 狀之合金，可使用為傳導性填充劑之金屬包括鋁、銦、錫、 鉛、鉍，以及在週期系統中第Π-Β至VII-B族之元素，包括 如辞、編、銃、欽、錯、叙、絡 ' 錮、嫣 '猛、鍊、鐵、 釕、锇、鈷、铑、錶、鎳、鈀、鉑等等。特別滿足於便利 性及相對便宜的是紹、辞、鐵、鎳、錫、錯、及銀。銅， 雖然具傳導性，可能存在為其會對抗某些橡膠複合調配物 之金屬形式。 一或多種碳黑和一或多種金屬粉末或顆粒之混合物可 被應用為任何相對之比例，例如：1:99至99:1之重量比例。 該填充劑可帶有或是含有各種之表面塗覆或是處理， 例如：砂炫、脂肪酸等等。 使用於實施本發明之傳導性填充劑包含至少1重量百 分比之該組成物，較佳係至少10及更佳為至少20。在該組 17 201132694 成物中最大量之填充劑的唯一限制係實際考量所給予的限 制，如：成本以及效能，但是典型地，一般之最大量為包 含少於4 0重5百分比之5亥組成物’更典型係少於3 5重量百 分比之該組成物。 添加劑 本發明之組成物也可含有添加劑β代表性之添加劑包 括但並非限定於抗氧化劑、固化劑、交聯助劑、固化助劑 以及焦化抑制劑、加工助劑、偶合劑、紫外線穩定劑（包括 紫外線吸收劑）、抗靜電劑、成核劑、抗黏劑、塑化劑(特別 是塑化劑油）、潤滑劑 '黏性控制劑、膠黏劑、抗黏著劑、 介面活性劑、增效劑油、酸清除劑、阻焰劑以及金屬減活 劑。這些添加劑典型係依習慣的方式使用為慣用的量，例 如：自0.01重量百分比或是少於20重量百分比或是更多，以 該組成物之重量為基礎。 適用之固化劑包括有機過氧化物、更適用的是那些在 大於120°C之溫度下具有1小時半生期的固化劑。可使用之 有機過氧化物範例包括1，1-二-第三丁基過氧基_3,3,5_三甲 基環己炫、過氧化一異丙苯、2,5-二甲基_2,5_二（第三丁基 過氧基）己烷、第三丁基過氧基異丙基笨、二-第三丁基過氧 化物，以及2,5-二甲基-2,5-二-(第三丁基過氧基）己烷。焦化 抑制劑包括2,2,6,6-四甲基°辰°定氧化物（TEMPO)以及4-經基 -2,2,6,6-四甲基哌啶氧化物（4_羥基丁丑]^0). 適用之紫外線穩定劑包括受阻胺光穩定劑(HALS)以及 紫外光吸收劑(UVA)添加劑。代表性之紫外光吸收劑(UVA) 18 201132694 添加劑包括苯并三α坐類型，例如：Tinuvin 326以及Tinuvin 328，可由汽巴公司購得。HAL’s和UVA添加劑之摻合物也 係有效的。抗氧化劑之範例包括受阻紛，如：四[伸曱基(3,5-二-第三丁基-4-羥基氫-肉桂酸酯）]曱烷；雙[(β-(3,5-二第三 丁基-4-羥基苯曱基）甲基羧基乙基)]-硫化物；4,4’-硫雙(2-曱基-6-第三丁基酚）；4,4'-硫雙(2-第三丁基-5-曱基酚）；2,2’-硫雙（4-曱基-6-第三丁基酚）；以及硫二乙烯雙(3,5-二-第三 丁基-4-羥基)-氫化肉桂酸酯；亞磷酸鹽及膦酸酯，例如： 三4-二-第三丁基苯基）亞磷酸鹽以及二-第三丁基膦酸 酉旨；硫化合物，例如：硫代二丙酸二月桂自旨、硫代二丙酸 二（十四烷醇）酯、以及硫代二丙酸二（十八烷醇）目旨；各種矽 氧烷；經聚合化之2,2,4-三曱基-1,2-二氫喹啉，η,η1-雙（1,4-二曱基苯基-Ρ-伸苯基二胺），經烷基化之二苯胺，4,4’-雙 (α,α-二甲基苯甲基)二苯胺，二苯基-Ρ-伸苯基二胺，經混合 之二-芳基-Ρ-伸苯基二胺，以及其它受阻胺類抗降解劑或穩 定劑。 加工助劑之範例包括但非限定於羧酸之金屬鹽類，例 如：硬脂酸辞或是硬脂酸鈣；脂肪酸如：硬脂酸、油酸或是 芥子酸；脂肪醯胺，如：硬脂醯胺、油酸醯胺、芥子醯胺 或是Ν,Ν'-乙烯雙硬脂醯胺；聚乙烯蠟；經氧化之聚乙烯蠟； 乙稀氧化物之聚合物；乙烯氧化物和丙稀氧化物之共聚 物；植物堪；石油堪；非離子性介面活性劑；聚石夕氧院流 體以及聚石夕氧烧。 19 201132694 複合作用 在一實施癌樣中，使用於實施本發明之組成物的成份 係被添加至一批式混合機或是用於熔融摻合之擠出器。該 等成份可以任何次序添加或是先製備一或多個用於和其它 成伤摻合之主要批次。在一實施態樣中，一傳導性填充劑 於一樹脂或是樹脂摻合物之主要批次係經製備且接著添加 至其它的樹脂。添加劑通常係在添加至該主體樹脂及/或填 充劑之前和一或多個其它成份摻合。典塑地該熔融摻合係 在最高熔融聚合物之上然而在低於過氧化物（若存在的話） 之活化溫度的溫度下執行。該經熔融摻合之組成物係接著 被遞送至一模型或是通過一沖模用以塑形為所欲之物件， 或是轉換為片狀、瞑狀或是某些其它用於儲存或是用以製 備供饋入於之後的塑形或加工步驟所用之材料的形式。一 偏好之物件係一經由射出成形方法而製造之經模製電氣物 件’在該方法中該經複合之材料係被饋入該射出成形機械 中以製造一規定設計之經模製部件。可擇地，若經塑形為 片狀或是某些相似之構形，接著該等片體等等可被塗覆上 —抗黏著劑以助於在儲存時易於處理。 複合該組成物可利用該技術領域中具有通常知識者所 知的標準設備而實現。複合設備之範例係内批次混合器， 例如：Banbury™或是Bolling™内混合器。可供選擇地， 可使用連續早一或疋雙螺旋混合器，例如：FarrelTM連續混 合器、Werner及PfleidererTM雙螺旋混合器，或是BussTM揉 合連續擠出器。所利用之混合器類型以及該混合器的運作 20 201132694 條件將影響該組成物的特性，例如：黏性、體積電阻率以 及擠出的表面光滑度。 可以各種類型的擠出器製備一含有包含本發明之組成 物之半導體層的料，例如：單—或雙職類型。這些組 成物必須具有在任何適用於熱·聚合物擠出設備之擠壓 性月匕。用於電線和纟覽線產品之最普遍的製造職係單一螺 旋塑化擠出器。對於慣用之單—螺旋擠出器之敘述可在美 國第4,857,6喊專利中找到。共擠壓以及擠出器之範例因 而可在美國第5,575,965號專利中發現。—典型之擠出器在 其上游端具有-進料斗且在其下游具有―冲模。聚合性複 合物之粒子通過一進料斗饋入該擠出器桶，其含有一具有 螺旋狀葉片之螺旋。擠出器桶及螺旋之長度對直徑的比例 典型係在約15:1至約30:1之範圍。在該下游端，在該螺旋底 端和該沖模之間，典型有一由阻流板支撐之過濾網組使用 於過滤由該聚合物溶融而來之任何大粒子污染物。該擠出 器之嫘旋部份典型係區分為三部份，固體饋入段、壓擠或 溶融段以及计罝供給或灌注段。聚合物之細粒係被傳送通 過該進料區進入該壓擠區，在壓擠區該螺旋通道的深度經 減少以壓縮該材料’而該熱塑性聚合物係藉由來自擠出器 桶之熱輸入以及由該螺旋所產生之摩擦剪應力之組合而被 熔化。大部份的擠出器具有多個延著該桶軸自上游往下游 連續之桶加熱區（多於二個）。各加熱區典型地具有分離的加 熱器以及加熱控制器以使得可建立延著該桶長度之溫度曲 線。在十字頭和沖模組裝處有額的加熱區，在該處由擠出 21 201132694 器螺旋所產生的壓力造成該熔化物流動且經塑形為電線和 纜線產物，該產物典型係垂直於該擠出器桶而移動。在塑 形之後，熱塑性擠出生產線典型地具有一水槽以冷卻及凝 固化該聚合物成為最終之電線或纜線產物，而接著用〆捲 轴捲取系統來收集長長的此產物。有很多電線和鐵線製邊 方法的變化’例如，有另外類型的螺旋設計，如：桶混合 器或其它類型，以及另供選擇的加工設備，如：聚合物傳 動泵用以產生排出壓力。在此揭露中所描述的組成物典裂 地可在任何適用於擠出電線及纜線組成物的製造設備上加 工0 絕緣層 在實施本發明中該典型係相鄰於該半導體層之絕緣層 係在該技術領域中已知的，其組成可以有廣泛的變化，且 其對於實施本發明並非是關鍵性的。舉例來說，該絕緣層 可包含一或多種之烯煙類彈性體、烯烴嵌段共聚物、 EPDM、EPR歧料氧烧，特狀__經官能化之聚稀煙， 例如：-經魏接枝之聚烯m經—或錄交聯劑交 聯之雜-烯烴共聚物，：端祕之聚錢I該絕緣層 可被填充或是未經填充的，且其典型係比該半導體層為 厚。代表性絕緣層係在美國第5 246,783號專利、 WO 00/41187及EP 1 619 217 A1 等文件中敘述。 以下範例係說明本發明之各種實施態樣。所有的部份 和百分比係以重量為計’除非另有指明。 特定實施態樣 22 201132694 樣品製備 所有的樣品係使用實驗室等級Brabender批次混合器 所製備。該混合器初始係設定為120°c且轉子速度為35轉/ 分鐘(rpm)。首先，將聚合物树脂裝填入该混合益中’而接 著緩慢地添加礙黑且混合15分鐘。每當可能的時候，先添 加聚烯烴及/或烴類橡膠’接著是碳黑’接著是非聚烯烴橡 膠，但是這並非是總是可以這樣做，因為某些組成物使得 此成為不可行而充滿該混合器。然而’在任何情況下，製 備一主要批次用於稍後之非烯烴橡膠添加。依據碳黑之級 別和樹脂的類型，在混合循環尾端之熔融溫度的範圍在130 至140°C之間。在某些實例中，其可能在該混合器中冷卻該 材料而不需移除；在其它實例中，則需要將該複合物由該 混合器移除用以在添加過氧化物之前先冷卻的目的。在此 實例中，該才料係經再裝填以添加過氧化物。在所有的實 例中，添加過氧化物之後，該混合物係於35rpm之下經額外 10分鐘的複合化以併入該過氧化物然而確定該複合物溫度 維持在125 C之下以避免過早的交聯。如此製備之複合物係 經壓縮模製為75密爾（mii)之板，且係在壓機（Wabash Model #30-1212-451-4ST MBX)中於175。(：下10分鐘以固化。樣品 係由該經固化之板經切割用以機械性質量測。該組成物成 份及其各別之特性係記述在第丨表中。比較例係記述在第2 表中且本發明之範例係記述在第3表。 體積電阻率測試樣品係藉由在熱塑性條件下壓擠模製 感興趣之複合物而製備之8 χ 2 χ 〇 75英吋的板。該樣品係 肩_*1: 23 201132694 經冷卻至室溫且由該模子中取出。扁平化之銅導體 (16 AWG)係在各板之各端包圍於該板之週圍所以該導體 係分隔2英吋，且各者係約距一板端為1英吋。將該經包圍 之板放回該8 X 2英吋模子，且該板係以該架設好之導體在 該壓機中於175°C下固化10分鐘。該板係接著經冷卻，由該 模子中取出且準備用於測試。 第1表 組成物成份以及其特性 樹脂 供應商 描述 密度 (g/cm3) 熔融係 數（12， 190°C) 門尼黏 度（ML 1+4, 100°C) 邵氏硬度 (Shore A) ENGAGE 7447 陶氏化學 乙烯/ 1-丁烯彈 性體 0.865 5.0 64 ENGAGE 7467 陶氏化學 乙稀/ 1-丁烯彈 性體 0.862 1.2 52 NORDELIP 3722 陶氏化學 烴類橡膠 0.880 18 71 NORDELIP 4640 陶氏化學 烴類橡膠 0.860 40 61 NORDEL IP3430 陶氏化學 烴類橡膠 0.860 44 54 SILASTIC GP-30 道康寧 聚矽氧烷 橡膠 1.090 N/A 34 SILASTIC 130-25 道康寧 矽橡膠 1.090 N/A 22 MILLATHANE 5004 TSE工業 聚胺曱酸 酯橡膠 1.210 50-70 60 24 201132694 密度由ASTMD-792-00，方法B量測 12 由 ASTMD-1238-04 (C 版本，條件 190°C/2.16 公斤）量測 門尼黏度由ASTM D-1646-94量測 邵氏硬度（Shore A)由ASTM D-2240量測 第2表 比較例 組成物，顯示為總量之重量百分比 比較例 比較例1 比較例2 比較例3 比較例4 ENGAGE 7447 63.40 ENGAGE 7467 20.64 Nordel IP3722 63.40 Nordel IP3430 29.48 50.85 碳黑（XC-500) 34.10 34.10 31.45 30.00 塑化劑（SUNPAR 2280) 0.00 0.00 14.74 15.00 氧化辞 1.97 2.00 過氧化二異丙苯 2.50 2.50 1.72 2.15 總量 100.0 100.0 100.0 100.0 邵氏硬度 85 90 67 55 張力@破裂（巴斯 卡） 3028 3079 1132 953 延長@破裂（°/〇) 291 145 689 653 M100(巴斯卡） 1306 2223 271 165 Trouser撕裂強度 (lbf/in) 26 14 56 43 體積電阻率（95°C，7天，歐姆-公分） 第1天 233 604 589 1758 第2天 246 582 577 1666 第3天 257 773 571 1615 第4天 400 747 567 1585 第5天 893 738 564 1564 第6天 1569 759 562 1544 第7天 2333 771 558 1534 邵氏硬度（Shore A)由ASTM D-2240量測 25 201132694 張力@破裂由ASTM D-63 8量測 延長@破裂由ASTM 63 8量測 ]\4100係由八8丁]\4〇-638量測 Trouser撕裂強度由ASTM D1938-08量測 體積電阻率由ASTMD-991量測 CE1表示一具有34.1 %碳黑和2.5°/。過氧化物之聚烯烴 類彈性體摻合物（密度0.865g/cm3，5 MI，邵氏硬度=64)之 資料。就應用而言’該複合物係十分堅硬，其具有邵氏硬 度為85，Ml 00為1306巴斯卡，雖然有良好的抗張強度，但 是卻有拙劣的延長為291%及拙劣的抗撕裂性。該體積電阻 率係不穩定的，初始為233歐姆-公分，接著在95°C下經7天 老化之後增加為超過2300歐姆-公分。 CE2表示一具有34.1%碳黑和2.5%過氧化物之烴類彈 性體摻合物（密度0.880g/cm3，邵氏硬度=71)之資料。就應 用而言，該複合物也是堅硬的，其具有邵氏硬度為90, M100 大於2000巴斯卡，雖然有良好的抗張強度，但是卻有拙劣 的延長為145%及拙劣的撕裂性。該體積電阻率係比CE1來 得穩定，初始為600歐姆-公分，接著在95°C下經7天之後僅 增加為771歐姆-公分。 CE3表示一具有31.45%碳黑、14.74%塑化劑油以改善 可撓性、1.97%氧化辞和1.72%過氧化物之聚烯烴類彈性體 (密度0.862g/cm3 ’ I.2 MI，邵氏硬度=51)和烴類橡膠（密度 0.860g/cm3 ’邵氏硬度為54)之摻合物的資料。該複合物呈 現明顯超過前二者之經改善的可撓性，其具有邵氏硬度為 26 201132694 67以及M1GG為27ι巴斯卡，且也有經改善的延長為689%， 良好的抗張強度以及明顯改善的抗撕裂性。在此層級的碳 黑之下，在9〇。(：下經7天之後，該體積電阻率也是穩定為 ~560歐姆-公分。 CE4表示一具有3〇%碳黑、15%塑化劑油、2%氧化鋅和 2.15%過氧化物之烴類橡膠（密度〇 86〇g/cm3,邵氏硬度為5句 之摻合物的資料。該複合物也呈現明顯超過先前範例之經 改善的可撓性，其具有邵氏硬度為55以及Mioo為165巴斯 卡’相對良好的抗張強度(953巴斯卡），良好的延長(653%) 以及良好的抗撕裂性。雖然在90。(：下經7天之後，該體積電 阻率係穩定為〜1550歐姆-公分’在此層級的碳黑之下，該 複合物於此應用並未能令人滿意的，在應用中該目標體積 電阻率係<1000歐姆-公分且較佳係<500歐姆-公分。 27 201132694 第3表 本發明之範例 組成物，顯示為總量之重量百分比 發明範例 範例1 範例2 範例3 範例 4 範例 5 範例 6 範例7 ENGAGE 7447 39.02 ENGAGE 7467 34.15 37.33 19.65 Nordel IP3722 Nordel IP3430 19.65 28.38 28.38 33.38 Millathane 5004 39.02 24.39 24.56 Silastic GP-30 17.68 35.00 Silastic 130-25 35.00 35.00 碳黑 (XC-500) 19.51 24.39 19.65 24.65 25.00 25.00 20.00 塑化劑 (Sunpar 2280) 14.63 14.73 14.73 7.50 7.50 7.50 氧化鋅 1.96 1.96 2.00 2.00 2.00 過氧化二 異丙苯 2.44 2.44 1.77 1.77 2.15 2.15 2.15 總量 100.0 100.0 100.0 100.0 100.0 100.0 100.0 邵氏硬度 79 69 67 60 59 56 46 張力@破 裂（巴斯 卡） 2367 952 1033 942 1023 961 1006 延長@破 裂(％) 309 561 659 833 335 443 578 M100 (巴 斯卡） 767 313 300 184 278 266 145 Trouser 撕 裂強度 (lbf/in) 80 52 54 43 17.3 18 26 體積電阻率（95°C，7天，歐姆-公分) 28 201132694 第1天 224 56 327 553 76 16 290 第2天 199 55 322 534 68 15 第3天 182 54 323 525 64 15 ^~25Γ~~ 第4天 156 54 328 520 61 15 242 第5天 123 54 333 515 59 16 237^ 第6天 104 54 340 512 58 17 ' ~~~233~' 第7天 95 54 347 507 57 19 230- 範例1表示一含有39°/。聚烯烴類彈性體（密度 0.865g/cm3，5 MI ’邵氏硬度=64)、39%之聚胺甲酸酯橡膠 (密度l_210g/cm3，邵氏硬度為6〇)、19.5%碳黑和2.44%過氧 化物之摻合物的資料。相較於比較例1，此複合物呈現邵氏 硬度為79、M100為767巴斯卡，高抗張強度，然而同等拙 劣的延長，但大量改善的抗撕裂性。然而，最重要地事實 是，雖然其使用比〜42%來得少之碳黑，在95。〇下經7天老 化之後’其具有較低且非常穩定的體積電阻率為〜1〇〇歐姆_ 公分。 範例2表示一含有34.15%聚烯烴類彈性體（密度 〇.862g/cm3，1.2 MI ’邵氏硬度=51)、24.39%之聚胺甲酸醋 橡膠（密度1.21〇g/cm3 ’邵氏硬度為60)、μ 63%塑化劑油和 2.44%過氧化物之摻合物的結果。該資料顯示經改善之邵氏 硬度為69、M100為313巴斯卡，良好抗張(952巴斯卡）以及 經改良之延長（561%)以及良好之抗撕裂性。如同範例2，其 僅使用24.4%之碳黑，在95。(：下經7天老化之後’該複合物 呈現一低且穩定的體積電阻率為〜55歐姆-公分。 範例3表示一含有37.3°/❶聚烯烴類彈性體（密度 0’862g/cm3，1.2 MI ’邵氏硬度=51)、24.56%之聚胺曱酸酉旨 橡膠（密度1.210g/cm3 ’邵氏硬度為6〇)、14 73%塑化劑油、 •mm. 29 201132694 19.65%碳黑、1_96%氧化辞和丨.”。/。過氧化物之摻合物的結 果。該資料顯示較低之複合物邵氏硬度為67、M1〇〇為3〇〇 巴斯卡，良好抗張（1033巴斯卡）以及經改良之延長（659〇/〇) 以及良好之抗撕裂性。如同範例2且甚至僅使用^65%之碳 黑，在95 C下經7天老化之後，該複合物具有一穩定的體積 電阻率為〜350歐姆-公分。 範例4表示一含有19.65°/。聚烯烴類彈性體（密度 0. 862旦/〇111，1.2]'41，邵氏硬度=51)、19.65%之烴類橡膠（密 度0.860g/cm3 ’邵氏硬度為μ)、17.68%聚矽氧烷橡膠（密度 1. 〇90g/cm3，邵氏硬度為34)、24.56%碳黑、14.73%塑化劑 油、1.96%氧化辞和1J7%過氧化物之摻合物的結果。該資 料顯示經進一步改善之邵氏硬度為60、M100為184巴斯 卡’良好抗張(942巴斯卡），高延長(833%)，以及良好之抗 撕裂性。如同範例2，其僅使用24.56%之碳黑，在95°C下經 7天老化之後，該複合物具有穩定的體積電阻率為〜52〇歐姆 -公分。這些結果應和比較例3(使用31.45碳黑，多於〜22%) 做比較。 範例5表示一含有28.3 8%烴類橡膠(密度〇·860g/cm3，邵 氏硬度=54)、35%之聚矽氧烷橡膠（密度1 .〇90g/cm3，邵氏硬 度為34)、25%碳黑、7.5%塑化劑油、2.0%氧化鋅和2.15% 過氧化物之摻合物的結果。相較於比較例4，該資料顯示， 僅使用25%之碳黑，在95。(：下經7天老化之後，該複合物具 有非常低及穩定的體積電阻率為〜60歐姆_公分。 範例6表示一含有28 π%烴類橡膠(密度〇.860g/cm3，邵 30 201132694 氏硬度-54)、35%之聚石夕氧烧橡膠（密度1 .(^Og/cm3，邵氏硬 度為22)、25%碳黑、7,5%塑化劑油、2.0%氧化鋅和215% 過氧化物之摻合物的結果。相較於比較例4，此複合物具有 相等之邵氏硬度為56，但是此資料再度顯示，僅使用25% 之碳黑，在95〇C下經7天老化之後，該複合物具有非常低及 穩定的體積電阻率為〜15歐姆-公分。考慮到此低體積電阻 率之情形下，此樣品之機械特性可以進一步被改良的。 範例7 s兒明複合物性質如何被平衡且表示一含有 33.38%經類橡膠（密度〇.86〇§/(；1113，邵氏硬度=54)、35%之聚 石夕氧院橡膠（密度l_090g/cm3，邵氏硬度為34)、20%碳黑' 7.5 %塑化劑油、2. 〇 %氧化鋅和2丨5 %過氧化物之摻合物的結 果。相較於比較例4，此資料顯示非常低之邵氏硬度為46， 較低之M100為145，但是最重要的，即使僅使用20%之碳 黑，在95°C下經7天老化之後，該複合物再度具有扑常低且 穩疋的體積電阻率為〜230歐姆-公分且相較於上方比較例5 及6具有經改良平衡的抗張、延長以及抗撕裂性。 雖然本發明係經由前述特定實施態樣以特定細節而被 敘述，此細節主要係用於說明之目的。一該技術頜域中具 有通$知識者可在不偏離如以下申請專利範圍所述之本發 明概念和範圍之下進行許多變化和改變。 【圖式簡單說^明】 (無） 【主要元件符號說明】 (無） 31Frisch) Polyamine phthalate article, in "Chemistry and Technology", η 册 ' Interscience Press, 1964 and so on. The polyoxyalkylene oxide and the amine phthalate rubber may be used singly or in combination with each other and are typically used in an amount ranging from 90 to 1% by weight, based on the weight of the composition. Preferably, the rubber is used in an amount ranging from 80 to 20% by weight, more preferably from 50 to 70% by weight, based on the mass of the composition. Conductive Filler Any conductive filler that will impart a volume resistivity of less than 1, 〇〇〇 ohm-cm to the semiconductor composition, preferably less than 500 ohm-cm and more preferably less than 250 ohms - The centimeters can be used to practice the invention. Representative conductive fillers include, but are not limited to, conductive carbon black and metal particles. The conductive carbon black may be selected from any of the carbon blacks listed in ASTM D-1765-76, including carbon blacks listed as per the ASTM designation: N110 N242 N326 N358 N568 N765 N121 N270 N327 N363 N601 N774 N166 N285 N330 N375 N650 N785 S212 N293 N332 N440 N660 N787 N219 N294 N339 N472 N683 N880 N220 S300 N347 N539 N741 N907 N231 S301 N351 N542 N754 N990 N234 S315 N356 N550 N762. Of course, any other carbon black of similar nature and which is suitable and effective for rubber compounding, such as: Ketjenblack EC, Vulcan C and XC carbon black, acetylene black and other so-called "conducting carbon black", similar to any of the above Newer carbon blacks, which may be assigned other names, and mixtures may also be included in the conductive carbon blacks that may be used in the practice of the present invention. 16 201132694 In one embodiment, the carbon black graphene is, for example, graphite, carbon nanotubes and/or fullerenes or a mixture thereof with other carbon blacks. The average particle size of such materials is typically at the nanometer scale. Optionally, or with a carbon black, at least one of the conductive metal powders or granules can be used as a conductive filler. These metal powders or granules typically have an average particle size of from 0.1 to 100 microns, more typically from 0.3 to 30 microns, measured by X-spectral line broadening. The metal particles/powder may have any desired particle shape, although as is known, the choice of the shape is determined by the intended end use for the metal filled product. A spherical shape, a plate shape, a prism shape, a filament shape, or the like can be used. Alternately or in combination with one or more other such metals or finely powdered alloys, metals that can be used as conductive fillers include aluminum, indium, tin, lead, antimony, and in the periodic system Elements of Group VII-B, including such as rhetoric, edifice, 铳, 钦, 错, 叙, ' ' 锢, 嫣 ' 猛, chain, iron, 钌, 锇, cobalt, 铑, phen, nickel, palladium, platinum, etc. . Particularly suitable for convenience and relatively inexpensive are Shao, rhetoric, iron, nickel, tin, wrong, and silver. Copper, although conductive, may be in the form of a metal that will fight certain rubber compounding formulations. A mixture of one or more carbon blacks and one or more metal powders or granules can be applied in any relative ratio, for example, a weight ratio of 1:99 to 99:1. The filler may be provided with or contain various surface coatings or treatments such as sand, fatty acids and the like. The conductive filler used in the practice of the invention comprises at least 1 part by weight of the composition, preferably at least 10 and more preferably at least 20. The only limitation of the maximum amount of filler in this group of 201132694 is the limits imposed by actual considerations, such as cost and performance, but typically the maximum amount is typically 5 mils containing less than 40 weights and 5 percentages. The composition 'more typically is less than 35 weight percent of the composition. Additives The composition of the present invention may also contain additives. Representative additives include, but are not limited to, antioxidants, curing agents, crosslinking assistants, curing assistants, and coking inhibitors, processing aids, coupling agents, and UV stabilizers. Including UV absorbers), antistatic agents, nucleating agents, anti-adhesives, plasticizers (especially plasticizer oils), lubricants, viscosity control agents, adhesives, anti-adhesives, surfactants, Synergist oil, acid scavenger, flame retardant and metal deactivator. These additives are typically used in conventional amounts in a conventional manner, for example, from 0.01 weight percent or less than 20 weight percent or more, based on the weight of the composition. Suitable curing agents include organic peroxides, more preferably those having a one hour half-life at temperatures greater than 120 °C. Examples of organic peroxides that can be used include 1,1-di-tert-butylperoxy_3,3,5-trimethylcyclohexanyl, cumene peroxide, 2,5-dimethyl _2,5-di(t-butylperoxy)hexane, tert-butylperoxyisopropyl stupid, di-tert-butyl peroxide, and 2,5-dimethyl-2 , 5-di-(t-butylperoxy)hexane. Coking inhibitors include 2,2,6,6-tetramethyl-t-oxide (TEMPO) and 4-carbyl-2,2,6,6-tetramethylpiperidine oxide (4-hydroxybutyrate) Ugly ^^). Suitable UV stabilizers include hindered amine light stabilizers (HALS) and ultraviolet light absorber (UVA) additives. Representative Ultraviolet Light Absorbers (UVA) 18 201132694 Additives include benzotriene alpha type, such as Tinuvin 326 and Tinuvin 328, available from Ciba. Blends of HAL's and UVA additives are also effective. Examples of antioxidants include resistance, such as: tetra [extension (3,5-di-t-butyl-4-hydroxyhydro-cinnamate)] decane; bis [(β-(3,5-) Di-tert-butyl-4-hydroxyphenylindenyl)methylcarboxyethyl)]-sulfide; 4,4'-thiobis(2-mercapto-6-t-butylphenol); 4,4' - thiobis(2-tert-butyl-5-nonylphenol); 2,2'-thiobis(4-mercapto-6-tert-butylphenol); and thiodiethylene bis(3,5- Di-t-butyl-4-hydroxy)-hydrocinnamate; phosphites and phosphonates, for example: tris-di-t-butylphenyl phosphite and di-t-butylphosphine Acid compounds; sulfur compounds, for example: dilaurin thiodipropionate, di(tetradecyl alcohol) thiodipropionate, and di(octadecyl alcohol) thiodipropionate; various Oxane; 2,2,4-trimethyl-1,2-dihydroquinoline, η,η1-bis(1,4-didecylphenyl-indole-phenylenediamine) An alkylated diphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, diphenyl-indole-phenylenediamine, mixed di-aryl - Ρ-phenylenediamine, and other hindered amine antidegradants or Given agent. Examples of processing aids include, but are not limited to, metal salts of carboxylic acids, such as: stearic acid or calcium stearate; fatty acids such as stearic acid, oleic acid or sinapic acid; fatty guanamines such as: Stearylamine, oleic acid amide, mustard amide or hydrazine, Ν'-ethylene bis-stearamide; polyethylene wax; oxidized polyethylene wax; polymer of ethylene oxide; ethylene oxide and Copolymer of propylene oxide; plant can be; oil can be; non-ionic surfactant; poly-stone oxygen hospital and polyoxan. 19 201132694 Combined action In an embodiment of the cancer, the ingredients used in the practice of the compositions of the present invention are added to a batch mixer or to an extruder for melt blending. The ingredients may be added in any order or one or more of the major batches for blending with other wounds may be prepared. In one embodiment, a conductive filler is prepared in a major batch of resin or resin blend and then added to other resins. The additive is typically blended with one or more other ingredients prior to addition to the host resin and/or filler. The melt blending is typically performed on the highest molten polymer, but at a temperature below the activation temperature of the peroxide, if present. The melt blended composition is then delivered to a mold or shaped into a desired article by a die, or converted to a sheet, a braid or some other for storage or use. To prepare a material for feeding into the subsequent shaping or processing steps. A preferred item is a molded electrical article manufactured by an injection molding process in which the composited material is fed into the injection molding machine to produce a molded part of a defined design. Alternatively, if shaped into a sheet or some similar configuration, the sheets or the like can then be coated with an anti-adhesive to facilitate ease of handling during storage. Compounding the composition can be accomplished using standard equipment known to those skilled in the art. An example of a composite device is an in-line batch mixer, such as a BanburyTM or a BollingTM internal mixer. Alternatively, a continuous early or double helix mixer can be used, such as a FarrelTM continuous mixer, a Werner and PfleidererTM double helix mixer, or a BussTM blend continuous extruder. The type of mixer utilized and the operation of the mixer 20 201132694 Conditions will affect the properties of the composition, such as viscosity, volume resistivity, and surface smoothness of the extrusion. A material containing a semiconductor layer comprising the composition of the present invention can be prepared by various types of extruders, for example, a single- or dual-duty type. These compositions must have any squeezing menstruation suitable for use in thermal polymer extrusion equipment. The most popular manufacturing grade single screw plasticizer for wire and wire products. A description of the conventional single-screw extruder can be found in the US Patent No. 4,857,6. Examples of co-extrusion and extruders are found in U.S. Patent No. 5,575,965. - A typical extruder has a - feed hopper at its upstream end and a "die" downstream of it. The particles of the polymerizable composite are fed into the extruder barrel through a feed hopper which contains a spiral having helical blades. The length to diameter ratio of the extruder barrel and the helix is typically in the range of from about 15:1 to about 30:1. At the downstream end, between the bottom of the helix and the die, a filter pack supported by a baffle is typically used to filter any large particulate contaminants that are melted by the polymer. The cyclone portion of the extruder is typically divided into three sections, a solid feed section, a squeeze or melt section, and a feed or fill section. A fine particle system of the polymer is conveyed through the feed zone into the crush zone where the depth of the spiral channel is reduced to compress the material and the thermoplastic polymer is heated by the barrel from the extruder The input and the combination of the friction shear stress generated by the spiral are melted. Most extruders have a plurality of barrel heating zones (more than two) that extend continuously from upstream to downstream of the barrel axis. Each heating zone typically has a separate heater and a heating controller such that a temperature profile extending the length of the barrel can be established. There is a heating zone at the crosshead and die assembly where the pressure generated by the extrusion 21 201132694 spiral causes the melt to flow and is shaped into wire and cable products, typically perpendicular to the wire. The extruder barrel moves. After shaping, the thermoplastic extrusion line typically has a water bath to cool and solidify the polymer into the final wire or cable product, and then the coiled-coil take-up system to collect the long product. There are many variations in wire and wire edge making methods', for example, there are other types of spiral designs, such as barrel mixers or other types, and alternative processing equipment such as polymer transfer pumps for generating discharge pressure. The composition described in this disclosure can be processed on any manufacturing apparatus suitable for extruding wires and cable compositions. 0 Insulating layer In the practice of the present invention, the typical system is adjacent to the insulating layer of the semiconductor layer. Known in the art, the composition thereof can vary widely, and it is not critical to the practice of the invention. For example, the insulating layer may comprise one or more olefinic elastomers, olefin block copolymers, EPDM, EPR oxy-combustion, specialized __ functionalized poly-smoke, for example: - Wei The grafted polyene m is crosslinked with a cross-linking hetero-olefin copolymer, and the insulating layer can be filled or unfilled, and is typically compared to the semiconductor layer. Thick. A representative insulating layer is described in U.S. Patent No. 5,246,783, WO 00/41187, and EP 1 619 217 A1. The following examples illustrate various embodiments of the invention. All parts and percentages are by weight unless otherwise indicated. Specific Implementations 22 201132694 Sample Preparation All samples were prepared using a laboratory grade Brabender batch mixer. The mixer was initially set at 120 ° C and the rotor speed was 35 revolutions per minute (rpm). First, the polymer resin was loaded into the mixture, and then the black was slowly added and mixed for 15 minutes. Whenever possible, add polyolefin and/or hydrocarbon rubber 'then carbon black' followed by non-polyolefin rubber, but this is not always possible because some compositions make this infeasible and full The mixer. However, in any case, a major batch was prepared for later addition of non-olefin rubber. Depending on the grade of carbon black and the type of resin, the melting temperature at the end of the mixing cycle ranges from 130 to 140 °C. In some instances, it may be possible to cool the material in the mixer without removal; in other examples, the composite needs to be removed from the mixer for cooling prior to the addition of peroxide. purpose. In this example, the material is refilled to add peroxide. In all of the examples, after the peroxide was added, the mixture was combined at 35 rpm for an additional 10 minutes to incorporate the peroxide. However, it was determined that the temperature of the composite was maintained below 125 C to avoid premature Cross-linking. The composite thus prepared was compression molded into a 75 mil (mii) plate and was at 175 in a press (Wabash Model #30-1212-451-4ST MBX). (: The next 10 minutes to cure. The sample was cut from the cured plate for mechanical quality measurement. The composition of the composition and its individual characteristics are described in the table. The comparative example is described in the second The table and examples of the invention are described in Table 3. The volume resistivity test sample is a 8 χ 2 χ 〇 75 inch plate prepared by compression molding a compound of interest under thermoplastic conditions. The sample shoulder _*1: 23 201132694 is cooled to room temperature and taken out of the mold. The flattened copper conductor (16 AWG) is surrounded by the end of each plate at each end so the system is separated by 2 inches.吋, and each is about 1 inch from the end of one of the plates. The enclosed plate is placed back into the 8 X 2 inch mold, and the plate is 175° in the press with the erected conductor. The film was cured for 10 minutes at C. The plate was then cooled, taken out of the mold and prepared for testing. Composition of the composition of Table 1 and its characteristics Resin supplier Describes density (g/cm3) Melting coefficient (12, 190° C) Mooney viscosity (ML 1+4, 100 ° C) Shore A ENGAGE 7447 Dow Chemical B / 1-butene elastomer 0.865 5.0 64 ENGAGE 7467 Dow Chemical Ethylene / 1-butene elastomer 0.862 1.2 52 NORDELIP 3722 Dow Chemical Hydrocarbon Rubber 0.880 18 71 NORDELIP 4640 Dow Chemical Hydrocarbon Rubber 0.860 40 61 NORDEL IP3430 Dow Chemical Hydrocarbon Rubber 0.860 44 54 SILASTIC GP-30 Dow Corning Polyoxane Rubber 1.090 N/A 34 SILASTIC 130-25 Dow Corning Rubber 1.090 N/A 22 MILLATHANE 5004 TSE Industrial Polyamine Terephthalate Rubber 1.210 50- 70 60 24 201132694 Density measured by ASTM D-792-00, Method B 12 Measured by ASTM D-1238-04 (C version, condition 190 ° C / 2.16 kg) Mooney viscosity measured by ASTM D-1646-94 Hardness (Shore A) was measured by ASTM D-2240. Comparative Example Composition of Table 2, showing the weight percentage of the total. Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ENGAGE 7447 63.40 ENGAGE 7467 20.64 Nordel IP3722 63.40 Nordel IP3430 29.48 50.85 Carbon black (XC-500) 34.10 34.10 31.45 30.00 Plasticizer (SUNPAR 2280) 0.00 0.00 14.74 15.00 Oxidation 1.97 2.00 Dicumyl peroxide 2.50 2. 50 1.72 2.15 Total 100.0 100.0 100.0 100.0 Shore hardness 85 90 67 55 Tension @ rupture (Baskar) 3028 3079 1132 953 Extension @ rupture (°/〇) 291 145 689 653 M100 (Basca) 1306 2223 271 165 Trouser tear strength (lbf/in) 26 14 56 43 Volume resistivity (95 ° C, 7 days, ohm-cm) Day 1 233 604 589 1758 Day 2 246 582 577 1666 Day 3 257 773 571 1615 4 days 400 747 567 1585 Day 5 893 738 564 1564 Day 6 1569 759 562 1544 Day 7 2333 771 558 1534 Shore A (Shore A) measured by ASTM D-2240 25 201132694 Tension @ Rupture by ASTM D- 63 8 measurement extension @rupture measured by ASTM 63 8]\4100 is measured by eight 8 butyl]\4〇-638 Trouser tear strength measured by ASTM D1938-08 volume resistivity measured by ASTM D-991 CE1 Indicates that it has 34.1% carbon black and 2.5°/. Information on peroxide-based polyolefin elastomer blends (density 0.865 g/cm3, 5 MI, Shore hardness = 64). As far as the application is concerned, the composite is very hard, with a Shore hardness of 85 and Ml 00 of 1306 Baska. Although it has good tensile strength, it has a poor elongation of 291% and poor tear resistance. Cracking. The volume resistivity was unstable, initially 233 ohm-cm, and then increased to over 2300 ohm-cm after 7 days of aging at 95 °C. CE2 represents a hydrocarbon elastomer blend having a density of 0.880 g/cm3 and a Shore hardness of 71 with 34.1% carbon black and 2.5% peroxide. In terms of application, the composite is also hard, with a Shore hardness of 90 and an M100 of more than 2000 Baska. Although it has good tensile strength, it has a poor elongation of 145% and poor tearing. . The volume resistivity was stable compared to CE1, initially 600 ohm-cm, and then increased to 771 ohm-cm after 7 days at 95 °C. CE3 represents a polyolefin elastomer with 31.45% carbon black and 14.74% plasticizer oil to improve flexibility, 1.97% oxidation and 1.72% peroxide (density 0.862g/cm3 'I.2 MI, Shao Hardness = 51) and data for a blend of hydrocarbon rubber (density 0.860 g/cm3 'Shore hardness 54). The composite exhibits an improved flexibility that significantly exceeds the former two, with a Shore hardness of 26 201132694 67 and an M1GG of 27 Å Baska, and an improved elongation of 689%, good tensile strength and Significantly improved tear resistance. Under this level of carbon black, at 9 〇. (: After 7 days, the volume resistivity is also stable to ~560 ohm-cm. CE4 represents a hydrocarbon with 3〇% carbon black, 15% plasticizer oil, 2% zinc oxide and 2.15% peroxide. Information on rubber-like blends (density 〇86〇g/cm3, Shore hardness of 5 sentences. The composite also exhibits improved flexibility over the previous examples, with a Shore hardness of 55 and Mioo For 165 Baska's relatively good tensile strength (953 psi), good elongation (653%) and good tear resistance, although at 90. (: after 7 days, the volume resistivity Stabilized to ~1550 ohm-cm" under this level of carbon black, the composite is not satisfactory for this application, in the application the target volume resistivity is < 1000 ohm-cm and preferably System < 500 ohm-cm. 27 201132694 Table 3 Exemplary compositions of the present invention, shown as weight percent of the total number of examples of the invention Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 ENGAGE 7447 39.02 ENGAGE 7467 34.15 37.33 19.65 Nordel IP3722 Nordel IP3430 19.65 28.38 28.38 33.38 Millathane 5004 39.02 24.39 24.56 Silastic GP-30 17.68 35.00 Silastic 130-25 35.00 35.00 Carbon black (XC-500) 19.51 24.39 19.65 24.65 25.00 25.00 20.00 Plasticizer (Sunpar 2280) 14.63 14.73 14.73 7.50 7.50 7.50 Zinc oxide 1.96 1.96 2.00 2.00 2.00 Dicumyl peroxide 2.44 2.44 1.77 1.77 2.15 2.15 2.15 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Shore hardness 79 69 67 60 59 56 46 Tension @rupture (Baskar) 2367 952 1033 942 1023 961 1006 extension@rupture (%) 309 561 659 833 335 443 578 M100 (Baskar) 767 313 300 184 278 266 145 Trouser tear strength (lbf/in) 80 52 54 43 17.3 18 26 volume resistivity (95° C, 7 days, ohm-cm) 28 201132694 Day 1 224 56 327 553 76 16 290 Day 2 199 55 322 534 68 15 Day 3 182 54 323 525 64 15 ^~25Γ~~ Day 4 156 54 328 520 61 15 242 Day 5 123 54 333 515 59 16 237^ Day 6 104 54 340 512 58 17 ' ~~~233~' Day 7 95 54 347 507 57 19 230- Example 1 shows a 39°/ . Polyolefin elastomer (density 0.865g/cm3, 5 MI 'Shore hardness=64), 39% polyurethane rubber (density l_210g/cm3, Shore hardness 6〇), 19.5% carbon black and 2.44% of the blend of peroxides. Compared to Comparative Example 1, the composite exhibited a Shore hardness of 79, a M100 of 767 kPa, a high tensile strength, but an equally prolonged elongation, but a greatly improved tear resistance. However, the most important fact is that although it uses less than ~42% less carbon black, at 95. After 7 days of aging, it has a lower and very stable volume resistivity of ~1 〇〇 ohm _ cm. Example 2 shows a polyurethane foam containing 34.15% polyolefin elastomer (density 〇.862g/cm3, 1.2 MI 'Shore hardness=51), 24.39% (density 1.21〇g/cm3 'Shore hardness is 60), the result of a blend of μ 63% plasticizer oil and 2.44% peroxide. The data shows an improved Shore hardness of 69, M100 of 313 pesa, good tensile (952 pesa) and improved elongation (561%) and good tear resistance. As in Example 2, it uses only 24.4% carbon black at 95. (: After 7 days of aging, the composite exhibits a low and stable volume resistivity of ~55 ohm-cm. Example 3 shows a polyolefin elastomer containing 37.3 °/❶ (density 0'862 g/cm3, 1.2 MI 'Shore hardness=51), 24.56% polyamine niobate tantalum rubber (density 1.210g/cm3 'Shore hardness 6〇), 14 73% plasticizer oil, • mm. 29 201132694 19.65% Carbon black, 1_96% oxidation and 丨.. The result of the blend of peroxides. This data shows that the lower composite Shore hardness is 67, M1 〇〇 is 3 〇〇 Baska, good Tensile (1033 Baska) and improved elongation (659〇/〇) and good tear resistance. As in Example 2 and even using only ^65% carbon black, after 7 days of aging at 95 C The composite has a stable volume resistivity of ~350 ohm-cm. Example 4 shows a polyolefin elastomer containing 19.65 ° / (density of 0. 862 denier / 〇 111, 1.2] '41, Shore hardness =51), 19.65% hydrocarbon rubber (density 0.860g/cm3 'Shore hardness μ), 17.68% polyoxyalkylene rubber (density 1. 〇90g/cm3, Shore hardness 34) The result of a blend of 24.56% carbon black, 14.73% plasticizer oil, 1.96% oxidation and 1J7% peroxide. The data shows a further improvement of Shore hardness of 60 and M100 of 184 Pascal' Good tensile (942 pesa), high elongation (833%), and good tear resistance. As in Example 2, it uses only 24.56% carbon black, after aging at 95 ° C for 7 days, The composite has a stable volume resistivity of ~52 ohm-cm. These results should be compared to Comparative Example 3 (using 31.45 carbon black, more than ~22%). Example 5 shows a 28.38% hydrocarbon rubber ( Density 〇·860g/cm3, Shore hardness=54), 35% polyoxyalkylene rubber (density 1. 〇90g/cm3, Shore hardness 34), 25% carbon black, 7.5% plasticizer oil, The result of a blend of 2.0% zinc oxide and 2.15% peroxide. Compared to Comparative Example 4, this data shows that only 25% carbon black is used at 95. (: After 7 days of aging, the composite The material has a very low and stable volume resistivity of ~60 ohm-cm. Example 6 shows a 28 π% hydrocarbon rubber (density 〇.860g/cm3, Shao 30 201132694 hardness -54 ), 35% of Ju Shixi Oxygen Burning Rubber (density 1. (^Og/cm3, Shore hardness 22), 25% carbon black, 7, 5% plasticizer oil, 2.0% zinc oxide and 215% The result of the blend of oxides. This composite has an equivalent Shore hardness of 56 compared to Comparative Example 4, but this data again shows that only 25% carbon black is used, and 7 days at 95 °C. After aging, the composite has a very low and stable volume resistivity of ~15 ohm-cm. The mechanical properties of this sample can be further improved in consideration of this low volume resistivity. Example 7 s shows how the properties of the complex are balanced and represent a rubber containing 33.38% warp rubber (density 〇.86〇§/(;1113, Shore hardness=54), 35% polyglycoside rubber (density l_090g) /cm3, Shore hardness of 34), 20% carbon black '7.5% plasticizer oil, 2. 〇% zinc oxide and 2丨5 % peroxide blend results. Compared to Comparative Example 4, This data shows a very low Shore hardness of 46, and a lower M100 of 145, but most importantly, even with only 20% carbon black, after 7 days of aging at 95 ° C, the compound has a bounce again. The often low and stable volume resistivity is 〜230 ohm-cm and has improved equilibrium tensile, elongation and tear resistance compared to Comparative Examples 5 and 6 above. Although the present invention is via the foregoing specific embodiments The details are described in detail for the purpose of illustration. One skilled person in the artisan can make many changes without departing from the inventive concept and scope as described in the following claims. And change. [Simple diagram of the figure] (none) [Description of main component symbols] (none) 31